DE3215259A1 - METHOD FOR THE PRODUCTION OF HIGH MOLECULAR POLYARYL SULFIDES, BRANCHED IF NEEDED - Google Patents

Description

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk

Central area 2 ? .. 04. 82

Patents, trademarks and licenses PS-by-c

Process for the production of high molecular weight, optionally branched polyarylene sulfides

Polyarylene sulfides and their preparation are known. (See for example US Patents 25 38 941, 25 13 188, 38 76 592, 33 54 129, DE-AS 24 53 749, DE-OS 26 23 363, US patents 40 38 261, 40 38 259, 40 38 263, DE-OS '26 23 362, US patent 40 38 262, DE-OS 26 23 333, US patents 40 64 114, 40 38 260, 40 39 518, JA-OS 55-54 330, Ja-OS 75 123 799, US patents 31 17 620, 35 24 835 and 38 39 301 and DE-OS 29 30 710 (Le A 17 603), DE-OS 29 30 797 (Le A 19 604) and DE-OS 30 19 732 (Le A 19 521)).

In many of these processes, high molecular weight, thermoplastically processable polyarylene sulphides are not obtained, you need a hardening or curing step that follows the reaction, in which chain lengthening and branching reactions the properties are improved.

If, according to the known process of the prior art, high molecular weight, thermoplastically processable Polyarylene sulfides are obtained (see the above

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DE-OS 29 30 710 (Le A 19 603), DE-OS 29 30 797 (Le A 19 604) and DE-OS 30 19 732 (Le A 19 521)) are special here Catalysts are required as well as to use reaction temperatures, which are often above the boiling point of the polar Solvent are, whereby the reaction must be carried out using excess pressure.

According to JA-PS 75 123 799, hexamethylphosphoric acid triamide is used as a co-solvent alongside N-methylpyrrolidone (2) in one Pressure reaction used in the production of polyarylene sulfides.

In US-PS 38 76 592 polyarylene sulfides are acid amides in phosphorus produced by reacting P ₇ S ₁ -, alkali or alkaline earth metal hydroxides and polyhalogenoaromatics. Thus, in a pressure reaction, in yields of less than 60%, based on the polyhalogen aromatic compound, polyarylene sulfides which are not of high molecular weight are produced.

In US patent 40 39 518, among other things, hexamethylphosphoramide as a solvent for the production of polyphenylene sulfide recommended, an exemplary embodiment is not available. In general, however, it is required that the Pressure must be sufficient to remove the p-dihalobenzene and the To keep amide essentially liquid (column 2, lines 64/66).

According to US Pat. No. 3,354,129, however, no thermoplastic properties are achieved even with batches at high temperatures and under pressure get processable products.

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In contrast, it has now been found that high molecular weight, optionally branched polyarylene sulfides are not used can be obtained from excess pressure if in a known manner polyhalogenoaromatics and alkali metal sulfides in cyclic organophosphorus compounds, preferably 1-alkyl-1-oxo-phospholanes, possibly in the presence a catalyst and / or a cosolvent condensed. The polyarylene sulfides obtained can be used without Curing step compression molded, extruded and spun into fibers.

The synthesis of these cyclic organophosphorus compounds is from the patent specifications EP-OS 0 006 and U.S. Patent 2,667,739.

The invention thus provides a process for the production of high molecular weight, optionally branched ones Polyarylene sulfides

a) Dihalobenzenes of which 50 to 100 mol% of the formula (I)

(D

correspond and 0 to 50 mol% of the formula (II)

R ¹

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whereby

X is fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and

R is identical or different and is hydrogen,

C ^ -C ₂₄ -alkaryl or C ^ -C ^ -aralkyl, and / or two radicals R can be linked to form an aromatic or heterocyclic ring, and always at least one
of hydrogen is, and

and always at least one radical R different

b) 0 to 2.4 mol%, preferably 0.4 to 2.0 mol%, based on on the dihalobenzenes, a tri- or tetrahalogen aromatic compound of the formula (III)

ArX _n (III)

whereby

Ar is an aromatic or heterocyclic radical with 6-24 C atoms,

X has the same meaning as in formula (I) and (II), and

η is 3 or 4, and

c) alkali sulfides, preferably sodium or potassium sulfide or a mixture thereof, preferably in the form of

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-Sf-

Hydrates or aqueous mixtures, optionally together with alkali metal hydroxides, the molar The ratio of (a + b): c in the range from 0.85: 1 to 1.15: 1, preferably 0.95: 1 to 1.05: 1, is in

d) an organic solvent, optionally with the use of catalysts and / or cosolvents, characterized in that the molar ratio of alkali sulfides c) to the organic solvent d) is in the range from 1: 2 to 1:15, cyclic organophosphorus compounds as organic solvent d) are used and the procedure for a reaction time of up to 10 hours, a reaction temperature of 160 ⁰ C to 240 ⁰ C, preferably from 165 ° C to 225 ⁰ C, without application is carried out by overpressure.

Substances which correspond to the prior art can be used as catalysts which may also be used in the Usual amounts can be used, for example alkali metal fluorides, alkali metal phosphates and alkali metal carboxylates mentioned.

As co-solvents to be used if necessary N, N-Dialky! Carboxamides of C.-Cjg-aliphatic and Cg-C. "- aromatic carboxylic acids in an amount of 0.02-1.0 mol, based on 1 mol of alkali metal sulfide, can also be used.

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The type and amount of the alkali sulfides to be used corresponds the state of the art. For example, lithium, sodium, potassium and rubidium sulfide are suitable, with Sodium and potassium sulfide are preferred. As, if necessary, to regenerate the alkali metal sulfides from possibly Alkali hydroxides to be used in the presence of hydrogen sulfides are LiOH, NaOH and KOH. It can be in both In cases, mixtures of both the sulfides and the hydroxides can also be used.

The alkali sulfides can be used in one or more steps, for example, by distilling off the water from the reaction solution, dewatered. The partial drainage should be completed prior to the addition of the p-dihalo compounds of formula (I) and (II).

N, N-dialkylcarboxamides possibly used as cosolvent are preferably used before the alkali metal sulfides are dehydrated. In principle, however, it is possible to add the cosolvents together with the polyhalogen compounds to the dehydrated batch.

In principle, the reactants can be combined in any form. The dihalo aromatics of the formulas (I) and (II) and the tri- or tetrahalogenoaromatics of the formula (III) can be used together or separately, continuously, in portions or directly at once to the alkali sulfide, the solvent or a part be given of it.

The molar ratio to be used according to the invention of meta- to para-dihalogenoaromatics of the compounds (I) or

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(II) should be a maximum of 30:70.

For the preservation of thermoplastically processable polyphenylene sulfides p-dihalogenoaromatics are particularly preferably used.

However, the alkali metal sulfide can also be used together with the solvent or part thereof to form the compounds of formulas (I), (II) and (III) are given. It is also possible to combine all of the reactants directly. Any other combination of reactants is also possible.

Examples of the aromatic dihalo compounds to be used according to the invention of formula (I) are: p-difluorobenzene, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 1-fluoro-4-chlorobenzene, 1-fluoro-4-bromobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 1,3-difluorobenzene, 1,3-dichlorobenzene, 1,3-dibromobenzene, 1,3-diiodobenzene, 1-fluoro-3-chlorobenzene, 1-fluoro-3-bromobenzene, 1-fluoro-3-iodobenzene, 1-chloro-3-bromobenzene, 1-chloro-3-bromobenzene, 1-chloro-3-iodobenzene and 1-bromo-3-iodobenzene. They can be used alone or in a mixture with one another. 1,4-dichlorobenzene and / or are particularly preferred 1,4-dibromobenzene.

Examples of the aromatic dihalo compounds to be used according to the invention of formula (II) are: 2,5-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dichlorobenzene, 1-ethyl-2,5-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4,5-tetramethyl-3,5-dichlorobenzene, 1-cyclohexyl-2,5-di-

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chlorobenzene, 1-phenyl-2,5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, 1-phenyl-2,5-dibromobenzene, 1-p-tolyl-2,5-dichlorobenzene, 1-p-tolyl-2,5-dibromobenzene, 1-hexyl-2,5-dichlorobenzene, 2,4-dichlorotoluene, 2,4-dichloroxylene, 2,4-dibromocumene, 1-cyclohexyl-3,5-dichlorobenzene and 1-phenyl-3,5-difluoro-benzene. You are alone or in a mixture can be used together.

Examples of the tri- or tetrahalogenoaromatics of the formula (III) are: 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,2,4-triiodobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 1,2,3-trichloronaphthalene, 1,2,4-tri-chloronaphthalene, 1,2,6-trichloronaphthalene, 2,3,4-trichlorotoluene, 2,3,6-trichlorotoluene, 1,2,3,4-tetrachloro-5 naphthalene, 1,2,4,5-tetrachlorobenzene, 2,2'-4,4'-tetrachlorobiphenyl, 1,3,5-trichlorotriazine.

Di-, tri- and tetrahalogen aromatic compounds can both simultaneously as well as separately added to the reaction phase.

Cyclic organophosphorus suitable according to the invention Compounds are p-substituted phospholanes and p-

substituted phosphines. Suitable p-substituents are C.-Cg-alkyls, Cg-C _12- aryls, C ₇ -C ₂₀ -aralkyls and C ₅ -C ₁₀ -cycloalkyls, preferably C.-C.-alkyls.

Cyclic organophosphorus compounds to be used with preference according to the invention are those of the formula (IV)

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(IV)

in the

R is a <L , tJ-butylene or oT, dJ-pentylene radical, which can also be substituted, but is particularly preferably a dC, cJ-butylene radical and

R a C.-C _g -alkyl-, a Cg-C .-- aryl-, a C ₇ -CQ-aralkyl radical or a C, _{-C .. 0} -cycloalkyl radical, particularly preferably a Cj- C. alkyl radical means.

According to the invention, preferred compounds of the Formula (IV) are 1-methyl-1-oxo-phospholane, 1-ethyl-1-oxo-phospholane, 1-phenyl-i-oxo-phospholane, 1-methyl-1-oxo-phosphane, 1-propyl-i-oxo-phosphane and 1-phenyl-1-oxo-phosphane called.

The reaction time can be up to 10 hours, preferably between 0.2 and 8 hours. One gradually Increasing the reaction temperature during this time is advantageous.

The pressure conditions during the reaction correspond to normal air pressure, which is an application of excess pressure not necessary, but can be done, with overpressures of 0.1 bar to 20 bar being possible.

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The work-up of the reaction mixture and the isolation of the polyarylene sulphides can be carried out in a known, varied manner Way.

The polyarylene sulfide can be taken directly from the reaction solution or only after addition, e.g. of water and / or dilute acids, are separated off according to the usual procedure, for example by filtration or by centrifugation.

The filtration is generally followed by the removal of inorganic constituents that cause the Polymers can adhere, such as residues of alkali sulfides and alkali chlorides, washing with water.

A wash or extraction with other washing liquids, which can also be carried out in addition to or after this wash is of course also possible.

The polymer can also be removed by removing the solvent from the reaction space and then washing, such as described above, can be obtained.

The polyarylene sulfides according to the invention can also with other polymers, such as pigments and fillers, such as graphite, metal powder, glass powder, Quartz powder or glass fibers mixed or with the usual additives for poly arylensulfide, such as customary stabilizers or mold release agents.

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In general, the behavior of Schitielzf is allowed PoIyarylensulfiden ASTM 1238-70 at 316 ⁰ C using a 5 kg weight, measured and reported in g / 10 minutes.

In the case of high melt flow values, however, this measurement can be carried out due to the high flow rate of the polymer melt To cause difficulties.

It was therefore the Schmelzviskositä-t £ 7 the polymer melt (in Pa.s) at 306 m ⁰ C as a function of the shear stress (in Pa.s) using the Instron Rotation determined.

In this way, the melt viscosity can be precisely determined in a very wide range from 10 to 10 Pa.s. In the Instrom rheometer, the polymer is sandwiched between a fixed plate and a rotatable cone melted and the torque of the cone determined. From the torque, the angular speed and the 'apparatus The melt viscosity can be calculated as a function of the shear stress. Used the rheometer model 3250 from Instron; Diameter of the cone and the plate 2 cm.

The melt viscosity is given, which is at a Shear stress of * £ = 10 Pa is measured.

The p-polyarylene sulfides according to the invention have direct after isolation from the reaction mixture generally melt viscosities of 0.5 10 to 5x10 Pa.s.

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3215253 -w-

or higher, but preferably from 1.5 10 to

4th
10 Pa.s. They can be processed directly by extrusion, extrusion blow molding, injection molding or other customary processing techniques into films, moldings or fibers, which are commonly used as automotive parts, fittings, electrical parts, e.g. switches, electronic panels, chemical-resistant parts and devices such as pump housings and pump impellers, Etching bath trays, sealing rings, parts of office machines and telecommunications equipment, as well as household appliances, valves, ball bearing parts, etc.

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Comparative example 1

For comparison, this example describes the preparation of polyphenylene sulfide according to US Pat. No. 3,354,129.

In an autoclave equipped with a stirrer, 129 g of sodium sulfide trihydrate (corresponding to 1 mol of Na "S) and 300 g of N-methyl-2-pyrrolidone were combined. The mixture was purged with nitrogen and slowly heated up to 202 ⁰ C. A total of 19 ml of water distilled off. The mixture was then cooled to about 16O ⁰ C and 147 g of p-dichlorobenzene (= 1 mol) g in about 50 N-methyl-2-pyrrolidone added. ^{The reaction mixture is heated to 245 °} C. in 30 minutes under the nitrogen pressure of 2.5 bar, the pressure rising to 10 bar, and this temperature is maintained for 3 hours. After cooling to room temperature, a gray solid is isolated, which is then subjected to careful washing with water to remove the inorganic impurities. It is dried at 80 ^° C. in a vacuum and 100.3 g (93%) of poly-p-phenylene sulfide with a light brown color and the following characteristics, melt viscosity, are obtained

ΛΛ U 2

I ^ = 4.5 Pa.s (at % = 10 Pa). Thermoplastic processing is not possible without hardening.

Comparative example 2

This example describes the production for comparison of p-polyphenylene sulfide according to JA-PS 55-54 330 (Asahi Dow K.K. dated 04/21/1980) Example 2.

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3215253

_ a.fl _

36.06 g (= 0.15 mol) of sodium sulfide nonahydrate and 150 ml of N, N'-dimethyethyleneurea were weighed into a 500 ml reaction _{vessel with an N 2 inlet and gas phase outlet.} The mixture was purged with nitrogen and slowly heated to 200-225 ⁰ C. This gave 25.9 g of distillate, which mainly consisted of water. After the reaction vessel had cooled, 22.15 g (= 0.15 mol) of p-dichlorobenzene were added. Under N ₂ ~ rinse was heated at normal pressure to 220 to 225 ⁰ C. After 4 hours the reaction mixture was poured into approximately 500 ml of methanol and the product separated by filtration. The crude product was distilled in about 1 liter for 4 hours. Water at 7O ⁰ C washed. After filtration, it was washed for 2 h at 5O ⁰ C in methanol, filtered and dried at 100 ⁰ C in vacuo. 9.39 (57.9%) light gray product with a melt viscosity of T) = 0.7 Pa. s (at t = 10 ² Pa) were obtained.

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example 1

48.7 g of sodium sulfide trihydrate (= 0.37 mol) and 2.64 g of NaOH dissolved in 19.2 g of H ~ 0 were initially introduced together with 150 g of 1-methyl-1-oxo-phospholane and the mixture at temperatures up to 210 ^° C dehydrated under an inert gas atmosphere. 38.7 g of a liquid which essentially consisted of water were distilled off. The batch was then cooled and dissolved in 35 g of 1-methyl-1-oxo with 56.85 g (= 0.387 mol) of p-dichlorobenzene and 1.07 g (1.6 mol%) of 1,2,4-trichlorobenzene -phospholane added. The mixture was then refluxed for 8 hours. The temperature rose in the reaction mixture from an initial 170 ⁰ C to 220 ⁰ C. After cooling, the batch was dissolved in 1 l of distilled water. Added water and separated the polyarylene sulfide after acidification by filtration. After vacuum drying at 120 ⁰ C 34.8 g (= 85.9% were bzg.

on sodium sulfide) product isolated.

μ> The melt viscosity was ^ = 3200 Pa.s ( L = 10

Pa).
Example 2

48.7 g sodium sulfide trihydrate, (= 0.37 mol) 2.64 g NaOH dissolved in 19.2 g H ₃ O and 18.9 g lithium acetate dihydrate (50 mol% or on sodium sulfide) were added together with 150 g 1- Methyl-1-oxo-phospholane submitted and dehydrated. The rest of the procedure - corresponded to Example 1. There were 32.4 g of product with a melt viscosity of

• 7? = 7860 Pa.s (at ^ = 10 ² Pa).

XXl

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Example 3

48.7 g of sodium sulfide trihydrate (= 0.37 mol), 10.05 g of NaOH dissolved in 25 g of H ₃ O and 16.1 g of dimethylacetamide (50 mol% or sodium sulfide) were added together with 150 g of 1-methyl-1 -oxo-phospholan presented and drained. The further procedure corresponds to Example 1. 33.6 g of product with a melt viscosity of T) = 11000 Pa.s (at ^ = 10 ² Pa) were isolated.

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Claims (4)

Claims Λ Process for the production of high molecular weight, possibly branched, polyarylene sulfides from a) Dihalobenzenes, of which 50 to 100 mol of the formula I. (D correspond, and O to 50 mol% of the formula II R ¹ R ¹ (ID R.
whereby 1 V-, 1 X fluorine, chlorine, bromine and iodine and R is identical or different and can be hydrogen, C .. -C ₂₀ -alkyl, C _{5 -C 20} -cycloalkyl, Cg-C ₂₄ -aryl, Cy-C ₂₄ -alkaryl or C ₇ -C ₂₅ -aralkyl, and / or two leftovers Le A 21 643 R to an aromatic or hetero cyclic ring can be linked, and always at least one radical R different of hydrogen is, and b) 0 to 2.4 mol%, based on the dihalobenzenes a tri- or tetrahalogen aromatic compound of the formula III ArX _n (III) whereby Ar is an aromatic or heterocyclic one Is a ring with 6-24 C-atoms, X has the same meaning as in formula I and II, and η is 3 or 4, and C) alkali sulfides, the molar ratio of (a + b): c in the range from 0.85: 1 to 1.15: located in d) an organic solvent, optionally with the use of catalysts and / or cosolvents, characterized in that that the molar ratio of alkali sulfides c) and organic solvents d) in the range from 1: 2 to 1:15, cyclic phosphorus Le A 21 643 organic compounds are used as the organic solvent d) and the process is carried out with a reaction time of up to 10 hours, a reaction ^{temperature of 160 °} C. to 240 ^° C. and without the use of excess pressure. 2. The method according to claim 1, characterized in that that the cyclic phosphorus compounds used are those of the formula IV R ² (IV) in the R is a co CJ-butylene or ex., 6 ^ -pentylene radical and R denotes a Cν * -Cg-alkyl, Cg-C .-- aryl, C ₇ -C ₃₀ aralkyl or C ₅ -C ^ cycloalkyl radical. 3. The method according to claims 1 and 2, characterized characterized in that one works at temperatures of 165 ⁰ C to 225 ⁰ C. 4. Process according to Claims 1 to 3, characterized in that compounds of the formula IV are Le A 21 643 2 ο 3 in which R is an oc, CJ-butylene radical and R is a C ₁ -C ₄ alkYl radical. Le A 21 643